Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

• the present invention relates to the use, for stabilizing polymers, in particular polyolefins, with respect to exposure to UV radiation, of fine-particle polymer powders comprising at least one UV absorber.
• the present invention further relates to stabilizer mixtures for stabilizing polymers with respect to exposure to UV radiation, oxygen and heat, which, inter alia, comprise these polymer powders, and to a process for stabilizing polymers, in particular polyolefins, with respect to exposure to UV radiation, oxygen and heat, which comprises adding, to the polymers, in particular to the polyolefins, an effective amount of these stabilizer mixtures.
• the present invention further relates to polymers, in particular polyolefins, which have been stabilized with respect to exposure to UV radiation or with respect to exposure to UV radiation, oxygen and heat, and which comprise an effective amount of these polymer powders or, respectively, stabilizer mixtures, and to articles produced from these stabilized polymers, in particular polyolefins.
• UV absorbers in order to stabilize polymers with respect to damaging exposure to UV radiation is a very general practice in the plastics-processing industry. Important factors here for longlasting protection are not only the long-term stability of the UV absorbers but also the stable dispersion of these in the polymer. This depends mainly on the compatibility of the UV absorber with the polymer used. If this is low, the consequence, in particular at the elevated temperatures encountered during processing, is very often undesired migration of the stabilizer to the polymer surface with resultant non-uniform stabilization of the polymer composition.
• the polymer powders comprising UV absorbers are usually obtainable via the intermediate stage of a polymer dispersion obtained through emulsion polymerization of a microemulsion, with a subsequent drying step.
• the preparation of colorant-containing polymer dispersions and of corresponding colorant-containing polymer powders is described in the specifications WO 99/40123, WO 00/18846, EP 1 092 416 A2, and EP 1 191 041 A2.
• colorants in the broader sense includes UV absorbers.
• polymers comprising these UV absorbers are used to formulate cosmetic compositions.
• the meaning of the expression that the polymer powders “comprise” the UV absorber(s) is that the UV absorber(s) may either have homogeneous distribution in molecular or microcrystalline form in the polymer matrix (to which reference is also made by way of example in lines 25-29 on page 3 of the specification WO 00/18846), or else has been completely or merely partially encapsulated by the polymer matrix. (“UV absorber” is used hereinafter in the singular even if according to the invention more than one UV absorber may be present in the polymer powder.)
• the UV absorber be (at least partially) soluble in the starting monomers used to prepare the polymer dispersions. It merely has to be wettable by the starting monomers or have been enclosed (at least partially) by the monomer droplets during the emulsion polymerization, and must have a suitable particle size distribution.
• UV absorber may, if necessary, be chemically modified using lipophilic radicals, as described in paragraphs [0012]-[0015] of the specification EP 1 092 416 A2.
• UV absorbers which may be used in the polymer powders are:
• 4-aminobenzoic acid and its derivatives in particular esters thereof, e.g. (ethoxylated)ethyl 4-aminobenzoate or 2-ethylhexyl-4,4-dimethylaminobenzoic acid;
• benzoates and salicylates e.g. phenyl salicylate, 4-isopropyl-benzyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, benzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, dibenzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate;
• substituted acrylates e.g. ethyl or isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate (mainly 2-ethylhexyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate), methyl ⁇ -methoxycarbonyl- ⁇ -phenylacrylate, methyl ⁇ -methoxycarbonyl- ⁇ -(p-methoxyphenyl)acrylate, methyl or butyl ⁇ -cyano- ⁇ -methyl- ⁇ -(p-methoxyphenyl)acrylate, N-( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl)-2-methylindoline, octyl p-methoxycinnamate, isopentyl 4-methoxycinnamate, urocanic acid and its salts and esters;
• 2-hydroxybenzophenone derivatives e.g. 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2′,4′-trihydroxy-, 2′-hydroxy-4,4′-dimethoxy-2-hydroxybenzophenone, and also sodium 4-methoxy-2-hydroxybenzophenone-sulfonate;
• esters of 4,4-diphenylbutadiene-1,1-dicarboxylic acid e.g. the bis(2-ethylhexyl)ester
• benzylidenecamphor and its derivatives as mentioned by way of example in DE-A 3 836 630, e.g. 3-benzylidenecamphor, 3-(4′-methylbenzylidene)-d1-camphor;
• dibenzoylmethanes e.g. 4-tert-butyl-4′-methoxydibenzoylmethane
• 2,4,6-triaryltriazine compounds e.g. 2,4,6-tris ⁇ N-[4-(2-ethylhex-1-yl)oxycarbonylphenyl]amino ⁇ -1,3,5-triazine, 4,4′-((6-(((tert-butyl)aminocarbonyl)phenylamino)-1,3,5-triazine-2,4-diyl)imino)bis(2′-ethylhexylbenzoate); and
• 2-(2-hydroxyphenyl)-1,3,5-triazines e.g. 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis-(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tria
• UV absorbers may be found in the publication Cosmetic Legislation, Vol. 1, Cosmetic Products, European Commission 1999, pp. 64-66, hereby incorporated herein by way of reference.
• the polymer powders used which comprise UV absorbers preferably have a polymer particle size ⁇ 500 nm.
• polymer powders which comprise from 0.5 to 50% by weight of the at least one UV absorber, based on the weight of the polymer matrix.
• Preferred stabilizer mixtures comprising component (a) and one or more of components (b) to (f) are those which comprise at least one polymer powder (a) whose polymer particle size is ⁇ 500 nm.
• other preferred stabilizer mixtures comprise at least one polymer powder(s) which comprises from 0.5 to 50% by weight of the at least one UV abosrber, based on the weight of the polymer matrix.
• Component (b) which is a possible constituent in the stabilizer mixtures of the invention, preferably comprises at least one organic phosphite, organic phosphine, or organic phosphonite selected from the group of the compounds of the formulae (VI) to (XV):
• Component (b) particularly preferably comprises at least one organic phosphite, organic phosphine, or organic phosphonite selected from the group of the compounds of the formulae (VI), (VII), (X), and (XI), where
• organic phosphites or organic phosphonites of component (b) are those selected from the group of compounds of the formulae (VI), (VII), (X), and (XI), where
• phosphites and phosphonites of component (b) are: triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl)phosphite (commercially available with the tradename Alkanox® TNPP; Great Lakes Chemical Corp.); trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite (commercially available with the tradename Alkanox® 240; Great Lakes Chemical Corp.); diisodecyl pentaerythritol diphosphite; bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (commercially available with the tradename Alkanox® P24;
• Possible components (b) which should be emphasized here in particular are the organic phosphites and phosphonites: tris(nonylphenyl)phosphite; tris(2,4-di-tert-butylphenyl)phosphite; bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite; tetrakis(2,4-di-tert-butylphenyl) 4,4′-diphenylenediphosphonite; and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
• organic phosphites and phosphonites listed above for component (b) are compounds known per se, many of which are commercially available.
• Sterically hindered phenols as possible component (c) of the stabilizer mixtures of the invention preferably comply with the formula (XIX)
• linear and branched C 1 -C 25 -alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylbutyl, pentyl, 1-methylpentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 1,3-dimethylbutyl, 2-methylpentyl, heptyl, isoheptyl, 1-methylhexyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, nonyl, isononyl, 1,1,3,3-tetramethylpentyl, decyl, 1,1,3-trimethylhexyl, isode
• R 1 ′ is preferably a methyl group or tert-butyl group.
• R 2 ′ is preferably a C 1 -C 20 -alkyl group, in particular a C 4 -C 18 -alkyl group.
• Particular definitions which should be emphasized for R 2 ′ are C 9 -C 18 -alkyl groups, and specifically here C 14 -C 18 -alkyl groups, e.g. octadecyl.
• R 2 ′ is usually a C 2 -C 10 -alkylene group, preferably a C 2 -C 8 -alkylene group.
• R 2 ′ is in particular a C 4 -C 8 -alkylene group, particularly preferably a C 4 -C 6 -alkylene group, e.g. hexamethylene.
• the alkylene groups may also contain one or more oxygen atoms or sulfur atoms.
• linear or branched C 2 -C 12 -alkylene groups are ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, and dodecamethylene.
• C 4 -C 12 -alkylene groups which contain one or more oxygen atoms or one or more sulfur atoms are —CH 2 —O—CH 2 CH 2 —O—CH 2 —, —CH 2 —(O—CH 2 CH 2 ) 2 —O—CH 2 —, —CH 2 —(O—CH 2 CH 2 ) 3 —O—CH 2 —, —CH 2 —(O—CH 2 CH 2 ) 4 —O—CH 2 —, and in particular —CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, and —CH 2 CH 2 —S—CH 2 CH 2 —.
• preferred sterically hindered phenols as possible component (c) are those where for n′′ equal to 1 in the formula (XIX) the radical R 2 ′ is a C 1 -C 20 -alkyl group.
• other preferred sterically hindered phenols as possible component (c) are those where for n′′ equal to 2 in the formula (XIX) the radical R 2 ′ is a C 2 -C 6 -alkylene group, a C 4 -C 8 -alkylene group which contains one or more oxygen atoms or one or more sulfur atoms, or, in the event that Y′′ is an —NH— group, a single chemical bond.
• sterically hindered phenols as possible component (c) are those where for n′′ equal to 4 in the formula (XIX) the radical R 2 ′ is one of the C 4 -C 6 -alkanetetrayl groups indicated above by way of example.
• sterically hindered phenols as possible component (c) in the stabilizer mixtures of the invention are those where in the formula (XIX) R 1 ′ is a methyl group or tert-butyl group, n′′ assumes a value of 1, 2, or 4, and X′′ is a group (XX), and Y′′ is an oxygen atom or an —NH— group, where for
• R 2 ′ is a C 14 -C 18 -alkyl group
• R 2 ′ is a C 4 -C 6 -alkylene group, or a C 4 -C 6 -alkylene group containing one or more oxygen atoms or containing one or more sulfur atoms, and
• R 2 ′ is a C 4 -C 6 -alkanetetrayl group.
• Sterically hindered phenols which are of interest as possible component (c) are those which have the formula (XIX) and which belong to the following listed group: N,N′-hexamethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (commercially available with the trademark Lowinox® HD-98; Great Lakes Chemical Corp.); octadecyl 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate (commercially available with the trademark AnoxTM PP18; Great Lakes Chemical Corp.); tetrakismethylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane (commercially available with the trademark AnoxTM 20; Great Lakes Chemical Corp.); triethylene glycolbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (commercially available with the trademark Lowinox® GP
• sterically hindered phenols preferred as possible component (c) in the stabilizer mixtures of the invention are those which contain a sterically hindered phenol group of the formula (I′) or (I′a)
• R′ 1 and R′ 2 independently of one another, are as defined above.
• the “compound” is composed of a mixture, composed of linear oligomers where R 1 is hydroxy and R 2 is hydrogen, and of cyclic oligomers where each of R 1 and R 2 is a single chemical bond, with an average molar mass of 3 900 g/mol.
• the sterically hindered phenols as possible component (c) are known, and in some cases are also commercially available. Others among these compounds may moreover be prepared, for example, as described in the specifications U.S. Pat. No. 3,330,859, U.S. Pat. No. 3,960,928, EP 162 523 A2, and EP 182 415 A2.
• Sterically hindered amines may also be present as further possible component (d) in the stabilizer compositions of the invention. At least one group of the formula (XXIII) or (XXIV)
• sterically hindered amines preferably those selected from the groups (a′) to (h′) of compounds listed below, and which have at least one of the abovementioned groups of the formulae (XXIII) or (XXIV).
• C 1 -C 12 -alkyl groups are: methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
• C 1 -C 18 -alkyl groups for G 11 and G 12 are: n-tridecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.
• Examples of C 3 -C 8 -alkenyl groups for G 11 are: 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, and 4-tert-butyl-2-butenyl.
• Propargyl is preferably used as C 3 -C 8 -alkynyl group for G 11 .
• a particular group which may be used as C 7 -C 12 -arylalkyl group for G 11 is phenylethyl, or preferably benzyl.
• C 1 -C 8 -alkanoyl groups for G 11 are: formyl, propionyl, butyryl, octanoyl, and in particular acetyl and, in the case of a C 3 -C 5 -alkanoyl group, preferably acryloyl.
• Examples of monovalent carboxylic acid radicals for G 12 derive from acetic acid, caproic acid (hexanoic acid), stearic acid (octadecanoic acid), acrylic acid, methacrylic acid, benzoic acid, and ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.
• Examples of monovalent silyl radicals for G 12 are: a radical of the formula —(C j H 2j )—Si(Z′) 2 Z′′, where j is an integer from 2 to 5 and Z′ and Z′′, independently of one another, are a C 1 -C 4 -alkyl group or C 1 -C 4 -alkoxyl group.
• Examples of bivalent dicarboxylic acid radicals for G 12 derive from malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid (octanedioic acid), sebacic acid, maleic acid, itaconic acid (methylenesuccinic acid), phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid, and bicycloheptenedicarboxylic acid.
• Examples of trivalent tricarboxylic acid radicals for G 12 derive from trimellitic acid, citric acid, and nitrilotriacetic acid.
• Examples of tetravalent tetracarboxylic acid radicals for G 12 derive from butane-1,2,3,4-tetracarboxylic acid and pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid).
• Examples of divalent dicarbamic acid radicals for G 12 derive from hexamethylenedicarbamic acid and 2,4-toluenedicarbamic acid.
• G is hydrogen
• G 11 is hydrogen or methyl
• G 12 is a diacyl radical of an aliphatic dicarboxylic acid having from 4 to 12 carbon atoms
• n is 2.
• polyalkylpiperidines of the formula (XXV) are:
• C 5 -C 7 -cycloalkyl use is preferably made of cyclohexyl.
• arylalkyl for G 13 use may be made of phenylethyl, preferably benzyl.
• C 2 -C 5 -hydroxyalkyl for G 13 use may be made of 2-hydroxyethyl and 2-hydroxypropyl, for example.
• C 2 -C 18 -alkanoyl for G 13 are: propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, and octadecanoyl. Mention should in particular be made of acetyl, and acryloyl is preferred if G 13 is C 3 -C 5 -alkenoyl.
• C 2 -C 8 -alkenyl for G 14 are: allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, and 2-octenyl.
• hydroxy-, cyano-, alkoxycarbonyl-, or carbamoyl-substituted C 1 -C 4 -alkyl are: 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl, and 2-(dimethylaminocarbonyl)ethyl.
• C 2 -C 12 -alkylene examples include: ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene.
• C 6 -C 15 -arylene examples include: o-, m-, or p-phenylene, 1,4-naphthylene, and 4,4′-diphenylene.
• C 6 -C 12 -cycloalkylene use may in particular be made of cyclohexylene.
• Preferred compounds of the formula (XXVI) are those where n is 1 or 2 and G is hydrogen, G 11 is hydrogen or methyl, G 13 is hydrogen, formyl, C 1 -C 12 -alkyl, or a group of the formula
• polyalkylpiperidines of the formula (XXVI) are in particular:
• Examples of C 2 -C 8 -alkylene or C 2 -C 8 -hydroxyalkylene for G 15 are: ethylene, 1-methylethylene, propylene, 2-ethylpropylene, and 2-ethyl-2-hydroxymethylpropylene.
• C 4 -C 22 -acyloxyalkylene for G 15 mention may be made of 2-ethyl-2-acetoxymethylpropylene.
• polyalkylpiperidines of the formula (XXVII) are in particular:
• C 1 -C 12 -alkyl examples include: methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.
• C 1 -C 18 -alkyl supplementary to the C 1 -C 12 -alkyl radicals listed by way of example above are: n-tridecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.
• C 2 -C 6 -alkoxyalkyl examples include: methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl, and propoxypropyl.
• Examples of C 3 -C 5 -alkenyl for G 17 are: 1-propenyl, allyl, methallyl, 2-butenyl, and 2-pentenyl.
• C 7 -C 9 -arylalkyl for G 17 , T 1 , and T 2 are: phenylethyl, preferably benzyl.
• T 1 and T 2 together with the carbon atom to which they are bonded form cycloalkane rings are:
• C 2 -C 4 -hydroxyalkyl for G 17 are: 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, and 4-hydroxybutyl.
• C 6 -C 10 -aryl for G 17 , T 1 , and T 2 are: unsubstituted or halogen- or C 1 -C 4 -alkyl-substituted phenyl, and unsubstituted or halogen- or C 1 -C 4 -alkyl-substituted ⁇ - or ⁇ -naphthyl.
• C 2 -C 12 -alkylene for G 17 are: ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylenes.
• Examples of C 4 -C 12 -alkenylene for G 17 are: 2-butenylene, 2-pentenylene, and 3-hexenylene.
• Examples of C 6 -C 12 -arylene for G 17 are: o-, m-, and p-phenylene, 1,4-naphthylene, and 4,4′-diphenylene.
• C 2 -C 12 -alkanoyl for Z are: propionyl, butyryl, octanoyl, and dodecanoyl, preferably acetyl.
• polyalkylpiperidines of the formulae (XXVIIIA), (XXVIIIB), and (XXVIIIC) are in particular:
• C 1 -C 12 -alkyl examples include: methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.
• C 1 -C 4 -hydroxyalkyl examples include: 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, and 4-hydroxybutyl.
• C 2 -C 6 -alkylene for A examples are: ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, and hexamethylene.
• G 21 and G 22 together form C 4 -C 5 -alkylene or C 4 -C 5 -oxyalkylene, mention should be made of: tetramethylene, pentamethylene, and 3-oxapentamethylene.
• polyalkylpiperidines of the formula (XXIX) are in particular:
• Group (f′) oligomers or polymeric compounds whose repeat units contain 2,2,6,6-tetramethylpiperidine radicals, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, and poly(meth)acrylamides, and also copolymers of these.
• 2,2,6,6-polyalkylpiperidines are determined by the following formulae, where m is a number from 2 to 200:
• polymeric compounds of the group (f′) are:
• Particularly important compounds for the purposes of the present invention are those which belong to the group (d) of the sterically hindered amines and have been selected from: Uvinul® 4049 H (BASF Aktiengesellschaft); Uvinul® 4050 H (BASF Aktiengesellschaft); Uvinul® 5050 H (BASF Aktiengesellschaft); Tinuvin®123 (Ciba Specialty Chemicals); Tinuvin®144 (Ciba Specialty Chemicals); Lowilite® 76 (Great Lakes Chemical Corporation); Lowilite® 62 (Great Lakes Chemical Corporation); Lowilite® 94 (Great Lakes Chemical Corporation); Chimassorb® 119 (Ciba Specialty Chemicals); Cysorb® UV 3529 (Cytec); Cyasorb® UV 3346 (Cytec); the compound of the formula (XXXV)-1:
• polymethylpropyl-3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]-siloxane commercially available with the trademark UVASIL® 299 (Great Lakes Chemical Corporation); polymethylpropyl-3-oxy-[4-(1,2,2,6,6-pentamethyl)piperidinyl]siloxane.
• the compounds of the group (d) of the sterically hindered amines used according to the invention have an average molecular weight M n of from 500 to 10,000, in particular from 1,000 to 10,000.
• the stabilizer mixtures may comprise at least one compound selected from the group of the chromanes. These compounds preferably have the formula (XXV)
• C 1 -C 24 -alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl (the above terms isooctyl, isononyl, isodecyl, and
• C 2 -C 24 -alkenyl groups vinyl, 1- and 2-propenyl, 1-, 2-, and 3-butenyl, 1-, 2-, 3-, and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl.
• Particularly preferred compounds of component (e) are 2,5,7,8-tetramethyl-2-(4′,8′,12′-trimethyltridecyl)chroman-6-ol( ⁇ -tocopherol),
• the stabilizer mixtures may comprise at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts.
• the oxidation state +2 is of importance for iron and manganese
• the oxidation state +3 is of importance for cerium.
• Preferred organic salts of zinc, calcium, magnesium, iron(II), and manganese(II) have the formula Me(An) 2
• preferred organic salts of cerium(III) have the formula Ce(An) 3
• Me is zinc, calcium, magnesium, iron(II), or manganese(II)
• An is an anion of an organic acid or of an enol.
• the acid may be linear or branched, saturated or unsaturated, aliphatic, aromatic, araliphatic, or cycloaliphatic, and may be unsubstituted or else may have substitution by hydroxy groups or by alkoxyl groups.
• the acid preferably contains from 1 to 24 carbon atoms. Examples of these organic acids are sulfonic acids, sulfinic acids, phosphonic acids, and phosphinic acids, and preferably carboxylic acids.
• carboxylic acids of this type are formic, acetic, propionic, butyric, isobutyric, caproic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, 2-, 3-, or 4-toluic, 4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic, and cyclohexylacetic acid.
• the carboxylic acid may also be a technical mixture of carboxylic acids, for example of fatty acids or of alkylated benzoic acids.
• organic acids which contain sulfur or contain phosphorus are methanesulfonic, ethanesulfonic, dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, benzenesulfinic, and naphthalenesulfonic acid, dodecanesulfinic, benzenesulfinic, and naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic acid, and monoalkyl esters thereof, and diphenylphosphinic acid.
• An is an enol anion, it is preferably an anion of a ⁇ -dicarbonyl compound or of an o-acylphenol.
• ⁇ -dicarbonyl compounds are acetylacetone, benzoylacetone, dibenzoylmethane, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate, and ⁇ -acetylcyclohexanone.
• o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetylnaphthol, 2-benzoylphenol, and salicylaldehyde.
• the enolate is preferably the anion of a ⁇ -dicarbonyl compound having from 5 to 20 carbon atoms.
• the anions present in organic salts of zinc, calcium, magnesium, iron(II), manganese(II), or of cerium(III) are preferably acetylacetonate or an aliphatic monocarboxylate having, for example, from 1 to 24 carbon atoms.
• Some of the particularly preferred salts are magnesium acetate, magnesium laurate, magnesium stearate, zinc formate, zinc acetate, zinc oenanthate, zinc laurate, zinc stearate, calcium acetate, calcium laurate, calcium stearate, manganese acetate, manganese laurate, manganese stearate, zinc acetylacetonate, calcium acetylacetonate, magnesium acetylacetonate, and manganese acetylacetonate.
• inorganic salts of zinc, calcium, magnesium, iron(II), manganese(II), and cerium(III): their oxides, hydroxides, and carbonates, and also, in the case of magnesium, naturally occurring or synthetic dolomite or hydrotalcite.
• the inorganic salts are used in the form of fine powders with average particle sizes of a few ⁇ m, preferably of a few nm.
• the fine-particle polymer powders comprising at least one UV absorber, and the stabilizer mixtures of the invention have excellent suitability for stabilizing polymers with respect to exposure to UV radiation and, respectively, with respect to exposure to UV radiation, oxygen and heat.
• Examples of polymers which may be stabilized by the polymer powders and, respectively, stabilizer mixtures are:
• the fine-particle polymer powders comprising at least one UV absorber, or the stabilizer mixtures of the invention may also be used in the preparation of polyurethanes, in particular in the preparation of polyurethane foams.
• the result is that the resultant polyurethanes and polyurethane foams are stabilized with respect to exposure to UV radiation or, respectively, with respect to exposure to UV radiation, oxygen and heat.
• polyurethanes One way of obtaining the polyurethanes is by reaction of polyethers, polyesters, and polybutadienes which contain terminal hydroxy groups with aliphatic or aromatic polyisocyanates.
• Polyethers having terminal hydroxy groups are well-known and may be prepared, for example, by polymerizing epoxides, e.g. ethylene oxide, propylene oxide, butylene oxide, styrene oxide, or epichlorohydrin, for example in the presence of boron trifluoride, or via an addition reaction of the epoxides, alone or in mixture with one another, or in a successive reaction using starters which contain reactive hydrogen atoms, e.g.
• polyethers which contain sucrose. In most cases preference is given to polyethers having a large number of primary OH groups (up to 90% of all of the OH groups present in the polyether). Use may also be made of polyethers modified using vinyl polymers, one method of preparing these polyethers being polymerization of styrene and acrylonitrile in the presence of polyethers which are polybutadienes having OH groups.
• the abovementioned compounds are polyhydroxy compounds and have molar masses in the range from 400 to 10,000 g/mol, in particular from 800 to 10,000 g/mol, preferably from 1,000 to 6,000 g/mol, the polyethers thus having, for example, at least two, usually from 2 to 8, but preferably from 2 to 4, hydroxy groups, and being thus known for the preparation of homogeneous polyurethanes and of cellular polyurethanes.
• Suitable compounds are aliphatic, cycloaliphatic, araliphatic, aromatic, or heterocyclic polyisocyanates, e.g. ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene 1,6-diisocyanate, dodecane 1,12-diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- or -1,4-diisocyanate, and also mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, hexahydrotolylene 2,4- and 2,6-diisocyanate and also mixtures of these isomers; hexahydrophenylene 1,3- and/or 1,4-diisocyanate, perhydrodiphenylmethane 2,4′- and/or 4,4′-diisocyanate
• distillation residues which contain isocyanate groups these residues arising during industrial production of isocyanates and being in undiluted form or dissolved in one or more of the abovementioned polyisocyanates. It is also possible to use any desired mixture of the abovementioned polyisocyanates.
• polyisocyanates which are easily obtainable industrially, examples of these being tolylene 2,4- and 2,6-diisocyanate, and also any desired mixture of these isomers (“TDI”); polyphenyl polymethylene polyisocyanates obtained by aniline/formaldehyde condensation followed by phosgenation (“crude MDI”); polyisocyanates containing carbodiimide groups, containing urethane groups, containing allophanate groups, containing isocyanurate groups, containing urea groups, and/or containing biuret groups (known as modified polyurethanes).
• TDI polyphenyl polymethylene polyisocyanates obtained by aniline/formaldehyde condensation followed by phosgenation
• CAMDI polyisocyanates containing carbodiimide groups, containing urethane groups, containing allophanate groups, containing isocyanurate groups, containing urea groups, and/or containing biuret groups (known as modified polyure
• paints are among the polymers which can be stabilized by the polymer powders comprising UV absorbers, or by the stabilizer mixtures of the invention.
• These binders are usually composed of, or comprise, one or more of the polymers described under the abovementioned points 1 to 29, in particular of one or more polymers described under points 20 to 25.
• the polymers which may be stabilized by the polymer powders comprising UV absorbers or by the stabilizer mixtures of the invention are preferably those naturally occurring, semi-synthetic or synthetic polymers selected from the groups described above.
• the polymer powders comprising UV absorbers, or the stabilizer mixtures of the invention are particularly used in the stabilization of thermoplastic polymers, preferably of polyolefins, particularly preferably of polyethylene and polypropylene, or their copolymers with mono- or diolefins.
• the present invention therefore also provides polymers, in particular polyolefins, stabilized with respect to exposure to UV radiation and comprising at least one UV absorber.
• the present invention also provides polymers, in particular polyolefins, stabilized with respect to exposure to UV radiation, oxygen and heat and comprising an effective amount of stabilizer mixtures of the invention.
• the present invention also provides articles produced from the abovementioned inventive polymers, in particular polyolefins, stabilized with respect to exposure to UV radiation and, respectively, stabilized with respect to exposure to UV radiation, oxygen and heat.
• Component (a) and the at least one other component selected from the group consisting of components (b) to (f) of the stabilizer mixtures of the invention may be either separate or else have been mixed with one another when added to the polymers.
• the amount of component (a) added to the polymers to be stabilized is from 0.0005 to 5% by weight, preferably from 0.001 to 2% by weight, and in particular from 0.01 to 2% by weight, based on the weight of the polymers to be stabilized.
• the amount of each of the components (b) and/or (c) and/or (d), and/or (e), and/or (f) added to the polymers to be stabilized is from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.025 to 3% by weight, and in particular from 0.025 to 1% by weight, based on the weight of the materials to be stabilized.
• components (a) and (b), and also, where appropriate, (c) and/or (d), and/or (e), and/or (f) of the stabilizer mixtures of the invention are added in the form of a mixture to the materials to be stabilized, their amounts present in the stabilizer mixtures of the invention are the amounts described above (based on the weight of the materials to be stabilized).
• Preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c) and also, where appropriate, other compounds selected from the group of components (d), (e), and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d) and also, where appropriate, other compounds selected from the group of components (c), (e), and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group of the chromanes as component (e), and also, where appropriate, other compounds selected from the group of components (c), (d), and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts, as component (f), and also, where appropriate, other compounds selected from the group of components (c), (d), and (e).
• Preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), and at least one compound selected from the group consisting of sterically hindered amines as component (d), and also, where appropriate, other compounds selected from the group of components (e) and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), and at least one compound selected from the group of the chromanes as component (e) and also, where appropriate, other compounds selected from the group of components (d) and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), and at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts, as component (f), and also, where appropriate other compounds selected from the group of components (d) and (e).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d), and at least one compound selected from the group of the chromanes as component (e), and also, where appropriate, other compounds selected from the group of components (c) and (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d), and at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts as component (f), and also, where appropriate, other compounds selected from the group of components (c) and (e).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group of the chromanes as component (e), and at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts, as component (f), and also, where appropriate, other compounds selected from the group of components (c) and (d).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), at least one compound selected from the group consisting of sterically hindered amines as component (d), and at least one compound selected from the group of the chromanes as component (e), and also, where appropriate, other compounds of component (f).
• Other preferred stabilizer mixtures comprise, besides components (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), at least one compound selected from the group consisting of sterically hindered amines as component (d), and at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts, and manganese salts as component (f), and also, where appropriate other compounds of component (e).
• the polymers may receive additions of undiluted UV absorbers, i.e. UV absorbers not embedded within a polymer matrix or partially or completely encapsulated by a polymer matrix, alongside the polymer powders comprising UV absorbers, and/or for the stabilizer mixtures of the invention to additionally comprise straight UV absorbers, for example those listed at the outset.
• undiluted UV absorbers i.e. UV absorbers not embedded within a polymer matrix or partially or completely encapsulated by a polymer matrix
• the stabilizer mixtures of the invention to additionally comprise straight UV absorbers, for example those listed at the outset.
• the stabilizer mixtures of the invention may moreover comprise other stabilizers (costabilizers), selected from the groups listed below.
• Tocopherols for example: ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and their mixtures (vitamin E).
• Hydroxybenzylated malonates for example: dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate;
• Benzylphosphonates for example: dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate; diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; the calcium salts of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols for example:
• esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols for example: methanol; ethanol; n-octanol; isooctanol; octadecanol; 1,6-hexanediol; 1,9-nonanediol; ethylene glycol; 1,2-propanediol; neopentyl glycol; thiodiethylene glycol; diethylene glycol; triethylene glycol; pentaerythritol; tris(hydroxyethyl)isocyanurate; N,N′-bis(hydroxyethyl)oxalamide; 3-thiaundecanol; 3-thiapentadecanol; trimethylhexanediol; trimethylolpropane; 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oc
• esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols for example: methanol; ethanol; n-octanol; isooctanol; octadecanol; 1,6-hexanediol; 1,9-nonanediol; ethylene glycol; 1,2-propanediol; neopentyl glycol; thiodiethylene glycol; diethylene glycol; triethylene glycol; pentaerythritol; tris(hydroxyethyl)isocyanurate; N,N′-bis(hydroxyethyl)oxalamide; 3-thiaundecanol; 3-thiapentadecanol; trimethylhexanediol; trimethylolpropane; 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oct
• esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols for example: methanol; ethanol; n-octanol; isooctanol; octadecanol; 1,6-hexanediol; 1,9-nonanediol; ethylene glycol; 1,2-propanediol; neopentyl glycol; thiodiethylene glycol; diethylene glycol; triethylene glycol; pentaerythritol; tris(hydroxyethyl)isocyanurate; N,N′-bis(hydroxyethyl)oxalamide; 3-thiaundecanol, 3-thiapentadecanol; trimethylhexanediol; trimethylolpropane; 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• Nickel compounds for example: nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine; triethanolamine or N-cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; nickel salts of monoalkyl esters; for example of methyl or ethyl ester; of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid; nickel complexes with ketoximes; e.g. with 2-hydroxy-4-methylphenyl undecyl ketoxime; nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole; with or without additional ligands.
• nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol] such as the 1:1 or 1:2 complex
• additional ligands such as n
• Oxamides for example: 4,4′-dioctyloxyoxanilide; 2,2′-diethoxyoxanilide; 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide; 2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide; 2-ethoxy-2′-ethyloxanilide; N,N′-bis(3-dimethylaminopropyl)oxamide; 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixtures with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide; and mixtures of disubstituted ortho- and para-methoxyoxanilides, and mixtures of disubstituted ortho- and para-ethoxyoxanilides.
• Metal deactivators for example: N,N′-diphenyloxamide; N-salicylal-N′-salicyloylhydrazine; N,N′-bis(salicyloyl)-hydrazine; N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine; 3-salicyloylamino-1,2,4-triazole; bis(benzylidene)oxalyl dihydrazide; oxanilide; isophthaloyl dihydrazide; sebacoyl bisphenylhydrazide; N,N′-diacetyladipoyl dihydrazide; N,N′-bis(salicyloyl)oxalyl dihydrazide; N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
• Hydroxylamines for example: N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; N,N-dialkylhydroxylamines derived from hydrogenated tall amines.
• Nitrones for example: N-benzyl- ⁇ -phenylnitrone; N-ethyl- ⁇ -methylnitrone; N-octyl- ⁇ -heptylnitrone; N-lauryl- ⁇ -undecylnitrone; N-tetradecyl- ⁇ -tridecylnitrone; N-hexadecyl- ⁇ -pentadecylnitrone; N-octadecyl- ⁇ -heptadecylnitrone; N-hexadecyl- ⁇ -heptadecylnitrone; N-octadecyl- ⁇ -pentadecylnitrone; N-heptadecyl- ⁇ -heptadecylnitrone; N-octadecyl- ⁇ -hexadecylnitrone; a nitrone derived from hydrogenated tall amines.
• Thiosynergists for example: dilauryl thiodipropionate; distearyl thiodipropionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl; stearyl; myristyl or tridecyl ester; mecaptobenzimidazole; or the zinc salt of 2-mercaptobenzimidazole; zinc dibutyldithiocarbamate; dioctadecyl disulfide; pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
• Polyamide stabilizers for example: copper salts in combination with compounds of iodine and/or of phosphorus, other examples being salts of divalent manganese.
• Basic costabilizers for example: melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, the alkali metal and alkaline earth metal salts of high-molecular-weight fatty acids, for example calcium stearate, zinc stearate, magnesium stearate, magnesium behenate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate, tin pyrocatecholate, zinc pyrocatecholate.
• Nucleating agents for example: inorganic substances, examples being talc, metal oxides, (such as titanium dioxide or magnesium oxide), phosphates, carbonates or sulfates (preferably of the alkaline earth metals); organic compounds, such as mono- or polycarboxylic acids and also their salts, (for example 4-tert-butylbenzoic acid, adipic acid; diphenylacetic acid; sodium succinate or sodium benzoate); polymeric compounds, such as ionic copolymers (“ionomers”).
• inorganic substances examples being talc, metal oxides, (such as titanium dioxide or magnesium oxide), phosphates, carbonates or sulfates (preferably of the alkaline earth metals); organic compounds, such as mono- or polycarboxylic acids and also their salts, (for example 4-tert-butylbenzoic acid, adipic acid; diphenylacetic acid; sodium succinate or sodium benzoate); polymeric compounds, such as ionic copolymers (“iono
• Fillers and reinforcing agents for example: calcium carbonate, silicates, glass fibers, glass beads, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour and other powders or fibers of other natural products, synthetic fibers.
• additives for example: plasticizers, dyes, pigments, lubricants, emulsifiers, rheological additives, catalysts, leveling assistants, optical brighteners, flame retardants, antistatic agents, blowing agents.
• stabilizers from 0.01 to 10% by weight of the abovementioned stabilizers (costabilizers), based on the weight of the polymers to be stabilized, may be added to the polymers to be stabilized.
• fillers and reinforcing agents described under item 11 such as talc, calcium carbonate, mica, or kaolin, based on the weight of the polymers to be stabilized, may be added to the polymers to be stabilized.
• fillers and reinforcing agents described under item 11 such as metal hydroxides, in particular aluminum hydroxide or magnesium hydroxide, based on the weight of the polymers to be stabilized, may be added to the polymers to be stabilized.
• carbon black filler based on the weight of the polymers to be stabilized, may be added to the polymers to be stabilized.
• the present invention also provides a process for stabilizing polymers, in particular polyolefins, with respect to exposure to UV radiation, oxygen and heat, which comprises adding, to the polymers, an effective amount of stabilizer mixtures of the invention.
• Components (a) and (b), and/or (c), and/or (d), and/or (e), and/or (f) are incorporated—individually or in a mixture with one another and, where appropriate, with other stabilizers (costabilizers)—into the polymers to be stabilized by methods known per se, e.g. prior to or during processing, or the stabilizer mixtures of the invention are dissolved or suspended in a solvent or suspension medium and added to the polymers to be stabilized prior to or after evaporation of the solvent or suspension medium.
• Masterbatches may also be prepared from the stabilizer mixtures of the invention, their content of these mixtures being from 2.5 to 25% by weight, based on the total eight of the masterbatch.
• the stabilizer mixtures of the invention where appropriate in the presence of other stabilizers (costabilizers), may be added, for example, after the polymerization process to the polymers to be stabilized, or else during the polymerization process, or prior to the crosslinking process.
• the stabilizer mixtures of the invention where appropriate in the presence of other stabilizers (costabilizers), may be in pure form, or else included within waxes, within oils, or within polymers, when added to the polymers to be stabilized.
• Stabilizer mixtures of the invention where appropriate in the presence of other stabilizers (costabilizers) capable of use in dissolved or molten form may also be sprayed into the polymers to be stabilized.
• This spray-addition process may advantageously be undertaken with the aid of the gas used to deactivate the polymerization catalyst, and together with the gas.
• the polymers stabilized according to the invention may be shaped in various ways, for example as films, fibers, tapes, melt compositions, profiles, or injection moldings.

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